Process for the dehydrogenation of hydrocarbons



n vMacl'l 20, 1945. E, BRENNAN 371,809

PROCESS FO THE DEHYDROGENATION-OF HYDROCARBONS HEATED RAW HYDROCARBON VAPORS a TREATED VAPORS -cATALYsT 8 INVENTOR H.e:.YDRENNAN HEATED RAW HYDROCARBON VA PORS carbon atoms.

Patented Man-2Q, 1945 r 'o'lFFlc-Ef PROCESS FOR THE DEHYDROGENATION F HYDROCARBONS nam E. Brennan, Bartlesville, om., assigner to Phillips Petroleum Company, a corporation 'of Delaware Application August 19, 1940, Serial No. 353,306 s claims. (cl. 2cm-ecm' This invention relates to the treatment of straight-chain hydrocarbons and in a more specic sense to a process for the catalytic dehydrogenation of paraflinic and olenic hydrocarbons to produce a. higher degree of unsaturation.' The invention is directed primarily to the treatment of such hydrocarbons having three to six carbon atoms although it may be applied also to hydrocarbons having six or more carbon atoms in chain arrangement.

While providing a process broadly applicable to the dehydrogenation of hydrocarbons such as are contained in or derived from petroleum and petroleum products, a particular object of the present invention is the conversion of the normally gaseous hydrocarbons asdefined above toy commercially valuable olens and/or diolens. Thisobject is accomplished with a practical minimum of undesirable side reactions.

The olens ofthe aliphatic series are valuable raw materials for many purposes. They are readily convertible into valuable products of industrial importance such as alcohols, ethersresters, glycols, acids and olen oxides. In addition the olefin polymerization and condensationproducts are useful as solvents and as fuels, and as components' which impart anti-knock qualities to fuel mixtures.

The mono-oleiins are of especial value as sources of dioleflns, the production of which involves a further dehydrogenation of mono-olefins yielding diolens with the same number of These dioleilns are readily 'utilized in the production of high molecular weight polymers and other valuable derivatives. Thus 35* a further object of this invention is to provide a process for the efficient conversion of mono-olenic hydrocarbons of the type described to diolens by catalytic idehydrogenation.'

The process according to the present invention comprises contacting a dehydrogenatable hydrocarbon containing from three to six carbon atoms to the molecule in vapor phase with a. solid adsorbent granular catalyst consisting of Y activated brucite at a suitable combination of temperature, pressure, and time of contact to control the character-and extent of the dehydrogenation. By this means I produce a practical yield oi olens and diolefinic'hydrocarbons depending on the charge stock, with a minimum of undesirable by-products and/or product losses.

I have found that the natural mineral ore, brucite, is a highly satisfactory catalyst `forthe selective dehydrogenation of the normally gaseing olenic hydrocarbons. Brucite is composed of a major proportion of hydrated magnesium oxide and minor proportions of compoundssuch as oxides of iron, silica, and the like. In the natural ore, the hydrated magnesium oxide or hy- Y droxide is presumably largelycolloidal inform,` and heating toremove a portion of the water of hydration converts the ore into a highly porous activated form with satisfactory hardness and resistance to shattering. The great extent of active surfaces thus obtained contributes to the hiiglh catalytic activity of the activated mater a In this connection I have found that activated brucite is f ar more active in promoting the conversion of hydrocarbons than magnesium oxide from other sources. Thus, synthetic magnesia preparations either in pill or powder form or supported inert carriers are inferior in catalytic activity to activated brucite. Similarly magnesia prepared from magnesite or other complex magnesium compounds does not have the catalytic activity of activated brucite. The peculiar physical structure and/ or the promoting action of the various components other than magnesium com- -pounds present in activated brusite apparently ing the peculiar physical structure of the ore. v

In the heating process, water is given off commencing at about 400 F. and continuing up to about 1500 F. and above. It is not lmown whether this upper limit represents the ultimate in' dehydration, but higher temperatures tend to powder the brucite and reduce it to a catalytically inactive form resembling synthetic magnesia. During the activation process, a slow, stream of inert gas may be passed through the heated mass to aid in the removal of water vapor. The activated brucite is thereby obtained as hard, Y

ous paraiiin hydrocarbons and of the correspondn pounds to hydrogen sulnde which is concurrently desorbed by the catalyst. Brucite retains its activity for promoting dehydrogenation reactions over relatively long periods of use at high temperatures. Also when there is a loss of kactivity due to tar and/or carbon deposition, the initial activity is readily and inexpensively restored by the removal of the organic deposits.

When the brucite catalyst has lost its activity to the extent that its use is no longer practical, it may be economically reactivated in place. The reactivation is accomplished by passing air or other suitable oxygen-containing gas through the heated material. Usually steam or other inert gas is added along with the oxygen-containing gas during reactivation in order to regulate the temperature of the operation by controlling the rate of combustion of the organic deposits. vTemperatures above 1500 F. are avoided since the activity o f the catalyst may be destroyed due to a change in physical structure. The catalyst may be repeatedly reactivated and its initial activity thus restored after each period of service.

The dehydrogenation of the low-boiling paraff drogenatable material may vary from 1:1 to 25:1 y

depending on the operating pressure. When temperatures near 1300 F. are used, water vapor is a suitable diluent, although at lower temperatures water vapor appears to aect the catalytic activity of brucite adversely and to shorten the active life of the catalyst.

The contact time oi reactants with the catalyst and hence the flow rate of the reactants is dependent on the particular hydrocarbon or hydrocarbon mixture being. treated, as well as on the operating temperature and pressure. With each particular hydrocarbon or mixture the temperature and flow rate can be so. regulated that sat# isfactory conversion is obtained with a minimum of cracking and decomposition of reactants and products. In general, ilow rates of the order of 1 to 10 liquid volumes of feed stock per hour per volume of catalyst are preferred. At higher temperature levels, shorter contact times are suilic cient, therefore still higher ilow rates may be n hydrocarbons containing three or more carbon atoms over activated brucite is preferably carried out -at temperatures within the range of 925 to about 120W F. yAt lower temperatures the catalyst is less active and satisfactory conversion is not obtained. At temperatures above 1300 F. prohibitively short contact times are required to suppress cracking reactions and the conversion of parailins to olens is low due to the fact that equilibrium is not attained in the dehydrognation reactions. Also, at the'higher temperatures above 1300 F. the catalyst is more rapidly deactivated by carbon deposition, and the process is more economically operated within the preferred temperature range and at contact times favoring equilibrium. a

High pressures are not necessary in my process as applied to parailln hydrocarbons, as excellent employed. t

According to one embodiment of my invention heated hydrocarbon vapors are passed at suitable ilow rates over a body of brucite catalyst maintained at temperatures between 925 and 1400 F. The eiliuents from the catalyst chamber containing dehydrogenated products and unconverted hydrocarbons along with lighter gases including hydrogen and small amounts of heavy polymer are then processed for the separation of the dehydrogenated product by fractional condensation or other suitable physical or chemical means, and the unconverted hydrocarbons may be returned for further conversion. Ii' a diluent is used, this may be separated from the light gases and hydrogen and recycled to the fresh feed stream. Alternately, the total` dehydrogenated mixture freefof fixed gases may be recycled for 40 further dehydrogenation until a suitable olefin results are obtained at moderate pressure be.

tween 0.3 and 20 atmospheres absolute. Usually it is desirable to operate at low super-atmospheric lpressures which will allow subsequent processing of the eilluent gases from the catalytic treatment but'which are not high enough to unfavorablyk influence the dehydrogenation reaction. I

The dehydrogenation .of the'low-boiling olefne such as the butenes over activated brucite is preferably carried out at temperatures in the higher portion of my temperature range, usually between about 1109 and 1400* F. At lower temperatures which may be satisfactory for dehydrogenating the paralns, I find` that suitable conversion of butenes is not obtained. At temperatures above l400 F. the suppression of decompositionreactions is more `difilcult and product losses are greater.

In the dehydrogenation ofolens, best results are obtained at atmospheric or sub-atmospheric pressures which help to suppress polymerization reactions and the like which involve the extr'emelyl reactive dioleiins. pressures may be obtained by vacuum operation or the like.

Another mode of operating at low effective partial pressures of the olenic material to be dehydrogenated comprises the addition thereto of a suitable gaseous diluent such as nitrogen, carbon dioxide, or a hydrocarbon gas substantially inert under operating conditions. When such a diluent is used, my process may be operated at pressures ranging from sub-atmospheric to 300 pounds gauge. The volume ratio of diluent to dehy- Sub-atmospheric concentration is built up.

The process of this invention is well adapted 'to a two-stage dehydrogenation operation whereby dioleiins may be produced from paraiiln hydrocarbons. Thus I may dehydrogenate a material such as normal butane over activated brucite at the conditions disclosed as most favorable for the paraiiin-olein conversion to produce a good yield of butenes. The butenes so produced may be then separated from unconverted butane, and dehydrogenated in a second step with activated brucite. The conditions for said second step conform to those disclosed as most favorable for the olefin-diolefln conversion. Alternately, the entire eiiiuent from the first step might be charged to the second step without prior separation of the butenes.

In view of the different conditions oftemperature for the two above-named conversions, and the necessity for using an inert diluent or subatmospheric pressure for the second step, I prefer to accomplish the conversion of parafiin to diolen in two separate steps, rather than in a single treatment, and therebyobtain more eili cient operation and better yields of diolen.

Further modiications of the process will be obvious to thosek skilled in the art and are held within the scope of the foregoing disclosure and the following operative examples.

Example I An activated brucite catalyst was prepared by grinding and sizing brucite to produce particles of approximately 8-20 mesh and calcining at about 1200 F. for two hours while passing a slow stream ot nitrogen through the bed. The nitrogen shortened the calclning time by aidingcin the dehydration. 'I'he resulting brucite catalyst was highwas packed in a tube having an insidefdiameter `of 18 mm. and a heatedlength of 65 cm.

The catalyst tube was maintained at a temperature of 1100 F. while n-butane vapor was two catalyst chambers or zones are used. These 1y porous and active. About 60fcc. of the catalystl passed through it at atmospheric pressures and v a iiow rate of 1 liquid volume of butalnel per hour per volume oi catalyst for a period'of four hours. Analysis of the eiliuent gas over the period of treatment showed an average conversion of n-butane to butenes of 25%. 4

To compare the activity of brucite with a synthetic magnesium oxide catalyst, n-butane was passed under conditions identical with those noted above over a catalyst consisting of magneslum oxide prepared by calcining magnesium carbonate. The conversion of n-butane was *decidedly lower, and the butenes produced amount to only 11%.

Example II An activated bruciteV catalyst prepared as noted in Example I was maintained at an average temperature of 1200 F. while a mixture of one part of butene-l and three parts of carbon l dioxide were passed through it at a ow rate equivalent to two liquid volumes of feed stock per hour per volume of catalyst. Samples of the eiiiuents during the run indicated an average conversion per pass of butene-l to butadiene correspending to about 15 per cent of the butene-l.

Example IH If desired, the hydrocarbon vapors may be given two or more successive treatments over the activated brucite catalyst in a series of towers or the vapors or any' fraction thereof may berecycled with fresh feed vapors through the catalyst tower. Care should be taken in the recycling of any vapors containing hydrogen that concentrations of hydrogen are not built up which will unfavorably iniiuence the reaction. In the case of successive treatments some additional heat may be supplied to the vapors prior to the second and/or successive passages over the catalyst.

Figure 1 represents schematically one type of apparatus inv which my process may be used. These drawings show fresh hydrocarbon feed vafpors entering a heater l vwhere they are raised to the desired treating temperature. From the heater the hot vapors pass directly to the catalyst chamber 2, and after passage over the catalyst, the treated vapors go to the fractionating unit 3. In the fractionating unit the vapors are fractionated to sendv the hydrogen and lighter hydrocarbons overhead while the heavier hydrocarbons pass to the unit l for extraction of dehydrogenated products. From 4 the unconverted hydrocarbons may be returned through the recycle line and pump 5 to the fresh feed line ahead oi the heater. Also a portion of the lighter gases may be recycled to the heater and catalyst chamber through pump 8.

Figures 2, 3 and 4 representschematically alternative forms of apparatus for the practice of the processes of the invention, wherein one and 'ngures represent portions of the complete apparatus shown schematically in Figure 1, and may be considered in connection with Figure 1 by interposition in the circuit in place of catalyst chamber 2. Figure -2 represents schematically apparatus for the recycling of part of the stream of hot treated vapors .for a second pass through the catalyst zone or' tower. In this instance, the stream of hot 'treated vapors leaving the catalyst zone or tower 8 is split, one part going through a vcompressor 1 (or its equivalent) wherein the pressure is raised just enough to force the rel cycled vapors into lthe stream of heated raw vapors prior to passage into the catalyst zone or tower. Figure 3'i1lustrates schematically apparatus for the practice of an alternative method for giving hydrocarbon vapors successive treatments in two catalyst zones or towers 9 and l0 in series together with the further alternative of recycling a portion of the hot treated vapors. Figure 4 illustrates schematically an apparatus for practicing amethod of supplying additional heat tothe hydrocarbon vapors leaving the first catalyst tower ll in heater I2 prior to passage 'through the second catalyst tower I3. Y

The foregoing speciiication and examples have disclosed and illustrated the invention, but since it is of wide application and the number of examples might be multiplied greatly, neither is to be construed as imposing limitations upon the scope of the invention. l

There is disclosed and claimed herein certain subject matter disclosed but not claimed in my prior United States 'Patent No. 2,181,877.

1. A process for the catalytic dehydrogenation of mono-olefinic hydrocarbons containing four to six carbon atoms to produce the correspond-Y of 1 to 10 liquid volumes of charge per hour per volume of catalyst, treating the eiuent vapors to obtain valuable diolenic products therefrom, and inally recycling the unconverted monooleiins to the catalyst.

2. A process for the catalytic dehydrogenation oi' paraiiln hydrocarbons containing four to sixcarbon atoms to produce the corresponding diolefins which comprises passing said hydrocarbons at pressures between atmospheric and pounds gauge over a catalyst consisting of brucite at temperatures within the range of 925 to 1200 F. and iiow rates of 1 to 10 liquid volumes of charge per hour per volume of catalyst to convert asubsftantial proportion of the paraflin charge to olens, treating the eiiluent vapors to segregate olens from unconverted parailins, recycling said unconverted parailins to the rst catalytic zone, passing said olens admixed with an inert diluent tofproduce partial pressures of olens of the order of 0.2 to one atmosphere at total pressures of from atmospheric to 50 pounds gauge over a catalyst consisting of brucite at temperatures within the range of 100 to 1400" F. and ow rates of 1 to 5 liquid volumes of charge per hour per volume 'of catalyst to convert a substantial proportion of oletlns to diolens, separating the resulting dioleflns from the unconverted oleilns, and recycling the latter with fresh oletln charge to the second catalytic zone.

3. vA process for the catalytic dehydrogenation.

of paraln and olefin hydrocarbons containing three to six carbon atoms to produce the correu destruction of the physical structure of. the brusponding oleflns and diolens which comprises contacting said hydrocarbons in vapor form with a catalyst consisting of brucite under conversion conditions of temperature and pressure such that a substantial dehydrogenation of-said hydrocarbons` without objectionable occurrence 'of cracking and decomposition reactions is obtained, the conversion temperature being in the range of 925 to 1400 F., said brucite having been prepared in active form by heating granular brucite ore at from 400 to 1500 F. in a stream of inert gas to remove a portion of chemically combined water and convert the brucite into a highly porous activated form with satisfactory hardness and resistance to shattering and without destruction of the physical structure oi the ore.

4. A process for the catalytic dehydrogenation of mono-olenic hydrocarbons containing four to six carbon atomsto produce the corresponding diolens which comprises passing said monoolens admixed with an inert diluent gas to result in a partial pressure of mono-olens of the order of 0.2 to 1 atmosphere at a total pressure between atmospheric and 50 pounds gauge over a catalyst consisting of activated brucite at a temperature within the range of 1100* to l400 F. and at a ow rate of from i to liquid volumes of charge per hour per volume of catalyst, said activated brucite catalyst having been prepared by heating granular brucite mineral at from 400 to 1500 F. in a stream of inert gas to remove a portion of chemically combined water and convert the brucite into a highly porous activated form with satisfactory hardness and cite, and thereafter treating the eiluent hydrocarbon vapors to recover valuable diolefinic products therefrom.

5. A process for lthe catalytic dehydrogenation of paramn hydrocarbons containing fourto six carbon atoms to produce the corresponding dioleilns which comprises passing said hydrocarbons at pressures between atmospheric and 100 pounds gauge over a catalyst consisting of activated brucite at atemperature withinthe range of 925 to 1200 'F. and at a ilow rate of from 1 to 10 liquid volumes of charge per hour per volume of catalyst. to convert a substantial proportion .of the, parafllns in the hydrocarbon charge to olens, said activated brucite catalyst having vbeen prepared by heating granular brucite mineral at 'from 400 to 1500 F. in a stream of inert gas to remove a portion of chemcalhr combined water and convert the brucite: into la highly porous activated form with satisfactory rating the resulting hardness and resistance to shattering and without substantial destructionY of the physical structure of the brucite; andV thereafter treating the etlluent hydrocarbon to segregate oleilns from unconverted'parafns, thereafter passing said oleiins admixed with an inert diluent to result in a partial pressure of olens of the order of 0.2- to 1 atmosphere at a total pressure between atmospheric and pounds gauge over` an activated brucite catalyst at a temperature within the range of 1100? to 1400 F. and at a ow rate of from 1 to 10 liquid volumes of charge per hour per volume of said catalyst to convert a substantial proportion of olens to dioleiins, and sepadiolefins from `the unconverted oleins.

HARRY E. `BRENNAN. 

